Near-Symmetry in our Universe:

The origin of life and the preponderance of matter

over antimatter

P. R. Bunker

Columbus 2008 Wednesday 18 June

+Ze

-e

Centre of Mass

One nucleus and one electron in a molecule

Fem

Molecular

Fem is the electromagneticforce between them

+Ze

-e +Ze

-e

C of Mass

PHem = HemP

Parity (or Inversion) Symmetry

FemFem’

Fem’ = Fem so

and parity (+/-) is a symmetry label.

+ Parity - Parity

x

Ψ+(x)

x

Ψ+(x)

x

Ψ-(x)

Ψ+(-x) = Ψ+(x)

Ψ-(-x) = -Ψ-(x)

Symmetry of eigenfunctionsrestricted by symmetry ofHamiltonian

A simple result of the Parity Symmetry of the

Ψ

Cs 7s(+) -------------

6s(+) -------------

Electric dipole transitionmoment = 0

This is completely forbidden as an electric dipole transitionsince the electric dipole moment μ has (-) parity.

∫Ψ+(7s)μΨ+(6s)dτ = 0

+Ze

-e +Ze

-e

C of Mass

PHew – HewP = δ

HOWEVER

FewFew’

Few’ ≠ Few

If we include the effect of the weak neutral current interaction

and parity (+/-) is not a perfect symmetry label

Parity Near-Symmetry or Parity-Violation

Cs 7s -------------

6s -------------

Electric dipole transitionmoment = 2.05(5) x 10-11 D

An ab initio ‘Standard Model’ calculation gives better than 1% agreement with experiment. See Dzuba et al., Phys Rev A 73, 022112 (2006)

Helectroweak mixes small amount of (-) parity states into each (+) state.

Wood et al., Science 275, 1759 (1997) and Can J Phys 77, 7 (1999).Linz et al., Eur Phys J A32, 525 (2007)

F = 4

F = 3

The effect of P-violation for a chiral molecule: CHFClBr

F

Cl

Br

F

Cl

Br

R SCF stretching frequency ν4 ~ 32 THz

Theory says ν4(R) ≠ ν4(S) because of parity-violation.

Enantiomers

Suggested in 1975 by V. Letokhov: Phys. Lett. 53A, 275 (1975); O.N.Kompanets et al, Opt. Commun. 19, 414 (1976); First experiment on camphor: Arimondo et al Opt. Commun. 23, 369 (1977), precision 10-8

Latest experiments CHFClBr: Ch.Daussy et al., Phys. Rev. Lett. 83, 1554 (1999); M. Ziskind et al,. Eur. J. Phys. D 20, 219 (2002): Strong 4 CF stretching mode which matches the R(14)-branch of the 9.4 m CO2 laser band (1071 cm-1). Resolution is a few Hz, and precision is about 10-13.

Experiments by Ch. Chardonnet and co-workers on CHFClBr

P-violation in chiral molecules

Suggested in 1975 by V. Letokhov: Phys. Lett. 53A, 275 (1975); O.N.Kompanets et al, Opt. Commun. 19, 414 (1976); First experiment on camphor: Arimondo et al Opt. Commun. 23, 369 (1977), precision 10-8

Latest experiments CHFClBr: Ch.Daussy et al., Phys. Rev. Lett. 83, 1554 (1999); M. Ziskind et al,. Eur. J. Phys. D 20, 219 (2002): Strong 4 CF stretching mode which matches the R(14)-branch of the 9.4 m CO2 laser band (1071 cm-1). Resolution is a few Hz, and precision is about 10-13.

Experiments by Ch. Chardonnet and co-workers on CHFClBr

P-violation in chiral molecules

Calculation of Δν4 for CHFClBr

Calculated frequency difference: Δν4 = ν4(R) – ν4(S) = 2.4 mHz Precision required: Δν4 / ν4 ~ 10-16

Trap molecule and use optical frequency comb

Deceleration of a large moleculein a high-field seeking state

Wohlfart, Grätz, Filsinger, Haak, Meijer, Küpper, Phys. Rev. A 77, 031404(R) (2008)

Talks TF10

and TG04

New ab initio calculations by D. Figgen and P. Schwertdfeger

Barrier Dip. Mom ΔEPV(S) Mol.Wt.

(cm-1) (D) (Hz) (u)

SOHF 23000 2.5 -0.012 68

SeOHF 19000 3.3 -0.10 116

SeOClI 8500 2.3 7.8 258

Need 1 D for every 20 u

New ab initio calculations by D. Figgen and P. Schwertdfeger

Barrier Dip. Mom ΔEPV(S) Mol.Wt.

(cm-1) (D) (Hz) (u)

SOHF 23000 2.5 -0.012 68

SeOHF 19000 3.3 -0.10 116

SeOClI 8500 2.3 7.8 258

Need 1 D for every 20 u

New ab initio calculations by D. Figgen and P. Schwertdfeger

Barrier Dip. Mom ΔEPV(S) Mol.Wt.

(cm-1) (D) (Hz) (u)

SOHF 23000 2.5 -0.012 68

SeOHF 19000 3.3 -0.10 116

SeOClI 8500 2.3 7.8 258

Need 1 D for every 20 u

Amino acid molecules are chiral

R R

L D

R = CH3, CH2OH, CH2SH, CH(CH3)2, …

Protein molecules

Protein molecules consist of up to about 10000 amino acid molecules joined together by peptide bonds.

Peptide bond

NH

CO

NH

CO

R

R’

The amino acid moleculesin proteins are all L

As a result all protein andDNA molecules are HELICAL

Also the sugar moleculesIn DNA are all D

There is “Homochirality”

How did Mother Nature arrange chemical evolution on the earth to give only L-amino acids and D-sugars?

HOMOCHIRALITY IS A BIG PROBLEM

Parity Violating Weak Neutral Current

Interaction causes E(D) ≠ E(L)

A Connection?

Biomols of Life are Homochiral (D-sugars and L-amino acids)

The Yamagata Hypothesis (1966)

E(D-sugars) < E(L-sugars), and

E(L-amino acids) < E(D-amino acids).

Leads to the required homochirality

Calculations reveal no clear evidence for this.And it ain’t so simple

See Wesendrup, Laerdahl, Compton and Schwerdtfeger, J. Phys. Chem. A 2003, 107, 6668.

No Connection (on Earth) with P-violation if Life

Came from Outer-Space!

Svente Arrhenius, Die Umschau 7, 481 (1903). “PANSPERMIA”

Palmer, Nature (1996) 383, 221.

Time before Present / 109 years

PO

2(atm

)

1

0.1

0.01

0.001

0.0001

0.000014.5 4 3.5 3 2.5 2 1.5 1 0.5 0

rise of O2

Earth begins (- 4.56 Gyr)

Life develops in < 0.5 Gyr?

Meteorimpacts

Nature 448,1005(2007)

FirstProkaryote(bacteria)

First Eukaryotes(cells contain a nucleus)

Fossil microorganismsIn Ontario, Canada.Tyler and Barghoorn,Science 119, 606 (1954)

First unambiguousevidence for life

Reduced 13C in rocks that formed more than 3.7 Gyr ago in Isua Greenland is possibly the oldest evidence of life on earth. Muchcontroversy. See Science 308, 366 (2005), Nature 434, 155 (2005).

Age of the earth: 4.56 Gyr:AllègrePhil Trans RSL.A 359, 2137 (2001)Wilde et al.Nature 409, 175 (2001)

Impacts on early earth:Nature 342, 139 (1989)Science 312, 1133 (2006)

300 ton/yr organic stuff5000 ton/yr 4.5 Gyr ago

Forming planets:Nature 448, 1003 and 1022 (2007)

ENERGETIC PREFERENCE• ΔE from parity violation, (Yamagata

1966).

BIOLOGICAL EVOLUTION• `Killer enzymes’

ENVIRONMENTAL EFFECT• Circularly polarized radiation, (Le Bel 1874, Van’t Hoff, Vester, Deutsch,

Bonner).• Formation on an asymmetric surface,

(Palache, Flores, Wächtershäuser, Hazen, Zepik).

STATISTICAL FLUCTUATION

Development of an Enantiomeric Excess

• Crystallization, (Landolt 1896, Viedma 2005)

• Autocatalytic reaction, (Strong 1898, Frank, Soai, Saghatelian

2001)

Amplification of an Enantiomeric Excess

Excess of one form Amplified by an

Autocatalytic Reaction

• Strong in Nature 59, 53 (1898). • Frank in Biochem. Biophys. Acta. 11, 459 (1953).

• Soai et al. in Nature 378, 767 (1995) and in The Chemical Record 1, 321 (2001), 2% excess of L-pyrimidyl alcohol amplified to

89%.

A + B L catalyzed by L inhibited by D

A + B D catalyzed by D inhibited by L

Excess of one form Amplified by an

Autocatalytic Reaction

• Strong in Nature 59, 53 (1898). • Frank in Biochem. Biophys. Acta. 11, 459 (1953).

• Soai et al. in Nature 378, 767 (1995) and in The Chemical Record 1, 321 (2001), 2% excess of L-pyrimidyl alcohol amplified to

89%.

A + B L catalyzed by L inhibited by D

A + B D catalyzed by D inhibited by L

LAST UNIVERSAL COMMON ANCESTOR (LUCA)

ENERGETIC PREFERENCE• ΔE from parity violation, (Yamagata

1966).

BIOLOGICAL EVOLUTION• Killer enzymes

ENVIRONMENTAL EFFECT• Circularly polarized radiation, (Le Bel 1874, Van’t Hoff, Vester, Deutsch,

Bonner).• Formation on an asymmetric surface,

(Palache, Flores, Wächtershäuser, Hazen, Zepik).

STATISTICAL FLUCTUATION

Development of an Enantiomeric Excess

Stereoselective Photochemical Reactions Caused by Circularly

Polarized Radiation

Bonner, Mayo Greenberg and Rubenstein in Origins of Life and Evol.of Biospheres 29,215 (1999): CP synchrotron radiation from electrons orbiting a neutron starshining on organic mantles of interstellar grains causes e.e. All 19L-amino acids absorb preferentially left-handed CPR in the UV.This extraterrestrial e.e. is then delivered to earth by interplanetary dust particles, comets or meteors.

CPR observed to have a weak stereoselective effect in the lab. .J.Phys.B 40,3425(2007),PRA 69,062717(2004),SPIE conf 2007

Bailey et al., Science 281 (1998) 672

Total Infrared intensity Percentage circular polarization

A star-forming region in the Orion nebula

arc sec

The Becklin Neugebauer object

Bailey et al., Science 281 (1998) 672

Total Infrared intensity Percentage circular polarization

A star-forming region in the Orion nebula

arc sec

Astronomical UV measurements with polarimeter needed!Astronomical UV observations with polarimeter needed

Bailey et al., Science 281,672(1998)

The Murchison meteorite has an e.e. of L-amino acids: Science 275, 951 (1997), Nature 394, 236 (1998)

Let‘s consider some other symmetries that are, or

might be, only near-symmetries

Implications in high res mol spec

+Ze

-e +Ze

-e

C of Mass

Inversion P

Force=F F’

Standard Model gives (F’ – F) to within 1%

PParity violation is understood

+Ze

-e -Ze

+e

C of Mass

CP

In the Standard Model (F” – F) is very small

Then charge conjugation C

F F”

+Ze

-e -Ze

+e

C of Mass

TCP

In Standard Model TCP is true symmetry

Then time reversal T

F F

+e

-e -e

+e

ν(1S-2S) in H = ν(1S-2S) in anti-H

TCP symmetry

H atom anti H atom

Proton

Electron

Positron

Anti proton

See Gabrielse et al, PRL 100, 113001 (2008) “Anti-H Production within a Penning-Ioffe Trap”

CP-Violation

CP-violation would account for the fact that the

universe does not consist of equal amounts of

matter and antimatter.

(Sakharov, Sov. Phys. JETP Letters, 5, 24 1967).

However, the Standard Model does not have enough CP-violation

See, for example, Trodden, Rev Mod Phys 71, 1463 (1999)

Measurement of CP-Violation

Can measure CP-violation using High Resolution Molecular Spectroscopy

Because of TCP symmetry lets talk in terms of T-violation

Hudson, Sauer, Tarbutt and Hinds, PRL 89 (2002) 023003

+

-

174YbF

Energies of mF = ±1 split by T-violation

Splitting Δ = 2 de Eeff

Electric dipole moment of an electron

Effective electric field at electron is huge in a heavypolar diatomic molecule

v=0, N=0 level has hfs with F = 0 and 1.

In an E-field F =1 has mF = 0 and ±1 components.

I(174Yb)=0, I(F)=1/2, ground state is 2Σ

174YbF

Δ = 2 Eeff de

= 2 x (25 GV/cm) x (~10-30 D) ~ 50 × 10-15 Hz

Quantum Chemical Calculation of Eeff for YbFMosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L763

In external field > 20 kV/cm they calculate Eeff = 25 GV/cm

So splitting of mF = ±1 levels is:Standard Model value of de

Δ = 2 Eeff de

= 2 x (25 GV/cm) x (~10-30 D) ~ 50 × 10-15 Hz

Quantum Chemical Calculation of Eeff for YbFMosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L763

In external field > 20 kV/cm they calculate Eeff = 25 GV/cm

So splitting of mF = ±1 levels is:Standard Model value of de

(5 x 10-19 D)

Minimal SupersymmetricStandard Model value of de

Δ = 2 Eeff de

= 2 x (25 GV/cm) x (5 × 10-19 D) ~ 24 mHz MSSM value of de

Quantum Chemical Calculation of Eeff for YbFMosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L763

Exp. limit |de| ≤ 10-17 D in PRL 89, 023003 (2002).

In external field > 20 kV/cm they calculate Eeff = 25 GV/cm

(An experiment on atomic Thallium gives |de| ≤ 10-18 D)

So splitting of mF = ±1 levels is:

Stark decelerator used: PRL 92, 173002 (2004)

See Hudson et al http://arxiv.org/pdf/physics/0509169

Δ = 2 Eeff de

= 2 x (25 GV/cm) x (5 × 10-19 D) ~ 24 mHz MSSM value of de

Quantum Chemical Calculation of Eeff for YbFMosyagin, Koslov and Titov, J. Phys. B. 31 (1998) L763

Exp. limit |de| ≤ 10-17 D in PRL 89, 023003 (2002).

In external field > 20 kV/cm they calculate Eeff = 25 GV/cm

(An experiment on atomic Thallium gives |de| ≤ 10-18 D)

So splitting of mF = ±1 levels is:

Stark decelerator used: PRL 92, 173002 (2004)

See Hudson et al http://arxiv.org/pdf/physics/0509169

Other CP-violation tests

Excited electronic state of PbO

Electric dipole moment of the neutron

Tevatron in Batavia Illinois

Large Hadron Collider at CERN

The Symmetrization Postulate

Another idea involves para-statistics and quons:See Greenberg and Delgardo, Phys Lett A 288, 139 (2001)

Can it breakdown?

Fermions: Only antisymmetric states Bosons: Only symmetric states

Pauli Exclusion Principle, nuclear spin stat. weightsand missing levels.

Fermi’s idea. They are not completely identical

One of the Failures of the Standard Model.

Exchange-symmetric states of He

Gordon Drake, Phys. Rev. A 39 (1989) 897.

Exchange symmetric states are called “paronic” states.

They violate the Pauli Exclusion Principle.

Gordon has calculated their energies.

Exchange-symmetric states of He

Atomic beam fluorescence experiment does not see transition from paronic state. Violation of PEP < 5 10–5. PRL 74, 4787 (1995)

Exchange-symmetric states of He

Exchange-antisymmetric states of CO2

For the CO2 molecule states with odd values of J

are missing because 16O nuclei are Bosons.

Mazzotti et al. PRL 86, 1919 (2001) looked for one:

Sensitivityshows thatprobability < 10–11

(0001)-(0000)R(25) calc at2367.265 cm-1

Exchange-antisymmetric states of CO2

For the CO2 molecule states with odd values of J

are missing because 16O nuclei are Bosons.

Mazzotti et al. PRL 86, 1919 (2001) looked for one:

Sensitivityshows thatprobability < 10–11

(0001)-(0000)R(25) calc at2367.265 cm-1

Molecular Spectroscopyand Near-Symmetry

P-violation

CP-violation

LifeE(L) ≠ E(D)

E( ) ≠ E( ) Matter

TCP-violation orSpin stat violation

Theoretical physics

Perfect Symmetry is

OK:Symmetry is one idea by which man has tried tocomprehend and create order, beauty and perfection.

Hermann

Weyl

But Near-Symmetry is Richer:

Irregularity is an essential feature of beauty, and that which is not slightly distorted is uninteresting. Charles P. Baudelaire

New ab initio calculations by D. Figgen and P. Schwertdfeger

Barrier1 Dip. Mom2 ΔEPV(S)3. (cm-1) (D) (Hz)SOHF 23000 2.5 -0.012 SeOHF 19000 3.3 -0.10 SeOClI 8500 2.3 7.8

1.One-component B3LYP using aug-cc-pVTZ basis.

2.Dirac B3LYP, uncontracted dual family basis sets of about augmented triple to quadruple zeta quality.

3.Dirac B3LYP calculation for S-enantiomer.

The Standard Model of particle physics

Particles: electron-neutrino, e, uq, dq muon-neutrino, muon, sq, cq tau-neutrino, tau, bq, tq [Aside: Proton is uud and neutron is udd ]

Forces: electromagnetic, weak and strong. Force carriers: hν, W, Z, gluon (all bosons)

Predicted: Higgs boson to give mass.

17 particles in all

Molecules

All fermions

Failures of Standard Model

Cannot explain fields responsible for inflation; Matter-antimatter asymmetry-not enough CP violation; Invisible cold dark matter-not SM theory particles ; Gravity; The values of the masses of the quarks and leptons; The symmetrization principle.

Various `extended’ supersymmetry theories devised and

these theories give more CP-violation than the SM (they still maintain TCP symmetry). They also explain inflation and dark matter, but not gravity,the masses of the fundamental particles (or the symmetrization principle).

Stereoselective Photochemical Reactions Caused by Magnetochiral

Dichroism• Wagnière and Meier: There is a difference in the absorption coefficients for enantiomers using unpolarized radiation in a magnetic field – a possible source for bio-homochirality.

Experientia 39, 1090 (1983).

• Rikken and Raupach: Nature 405, 932 (2000). Cr(III)tris-oxalato complex: D and L forms. Spontaneously

dissociates and re-associates in solution. Light accelerates this dissociation. In a magnetic field one form absorbs more strongly; the more absorbing form dissociates more often but re-association forms equal amounts of each and we get an e.e. of less-absorbing form. If we change the direction of

magnetic field we get an excess of the other enantiomer.

Stereoselective Chemistry on a Surface

• Palache et al. 1962: Quartz.

• Flores and Bonner 1974: Kaolin.

• Wächtershäuser 1993: Iron pyrite

• Hazen et al. 2001: Calcite

• Zepik et al. 2002: Reaction at water surface

“Polymerization on the Rocks: Theoretical Introduction”by Leslie Orgel in Origins of life 28, 227 (1998):“Impossible to synthesize long polymers of amino acids, nucleotides etc., in homogeneous aqueous solution. We suggest pre-biotic synthesis on a mineral surface”

Enantiomeric Excess amplified by

Crystallization • Landolt in Ber. d. deutsch. chem. Ges. 1896, p. 2410:

One can precipitate crystals from aqueous sodium chlorate solution by adding alcohol. Equal amounts of minute l and d crystals are obtained. However, if add a little alcohol VERY SLOWLY get an e.e. In this latter case only a few seed crystals formed for which l/d is not exactly equal to one.

• Kondepudi (1990) and Viedma (2005):

Achieve same result by stirring a crystallizing solution to stop formation of many seed crystals.

It is a competition between primary and secondary nucleation. If the experiment is repeated many times then the sum of allexperiments will give a 50:50 mixture of enantiomers.

Frank, Bonner and Zare, in `Chemistry for the 21st Century,’ Eds Keinan and Schecher,Wiley

(2000)

“Credible mechanisms have been identified for the extraterrestrial production and delivery to early Earth of organic molecules and amino acids containing a small e.e. The subsequent terrestrial sequestration of an initial e.e. and its amplification into dominance are processes for which biogenetically credible mechanisms exist.”